Method of killing nematodes with bis (1, 2-dichloroethyl) sulfone



United States Patent 3,362,870 METHOD OF KILLING NEMATODES WITH BIS (1,2-DICHLOROETHYL) SULFONE Paul C. Aichenegg, Kansas City, Mo., assignor to Chemagro Corporation, New York, N.Y., a corporation of New York No Drawing. Filed Mar. 5, 1965, Ser. No. 437,550

1 Claim. (Cl. 167-22) This invention relates to the control of fungi.

It is an object of the present invention to combat fungi.

Another object is to combat soil borne fungi.

A further object is to combat nematodes.

Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

It has now been found that these objects can be attained by applying to the fungi or their habitat, e.g. soil bis (1,2-dichloroethyl) sulfone having the formula ClOH OHClSO CHClCH Cl Bis (1,2-dichloroethyl) sulfone has two asymmetric carbon atoms and exists in at least two isomeric forms. Both forms are effective as fungicides.

The bis (1,2-dichloroethyl) sulfone can be used alone as a fungicide or nematocide but it has been found desirable to apply it to the pest or its habitat, together with inert solids to form dusts or suspended in a suitable liquid dileunt, e.g. water. It can be applied at widely varying rates, e.g. 0.1-30 lbs/acre of the active ingredient.

There can also be added surface active agents or wetting agents and inert solids in such liquidformulations. Desirably, 0.054% 'by weight of surface active or wetting agent is employed. The active ingredient can be from 0.01 to 95% by weight of the entire composition in such case.

In place of water there can be employed organic solvents as carriers, e.g., hydrocarbons such as benzene, toluene, xylene, kerosene, diesel oil, fuel oil, and petroleum naphtha, ketones such as acetone, methyl ethyl ketone and cyclohexanone, chlorinated hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene and perchloroethylene, esters such as ethyl acetate, amyl acetate and buty-l acetate, ethers, e.g., ethylene glycol monomethyl ether and diethylene glycol monomethyl ether, alcohols, e.g., ethanol, methanol, isopropanol, amyl alcohol, ethylene glycol, propylene glycol, butyl carbitol acetate and glycerine. Mixtures of water and organic solvents, either as solutions or emulsions, can be employed.

The novel pesticide can also be applied as an aerosol, e.g., by dispersing them in air by means of a compressed gas such as dichlorodi-fluoromethane or trichlorofluoromethane and other Freons, for example.

The pesticide of the present invention can also be applied with nematocidal and fungicidal adjuvants or carriers such as talc, pyrophyllite, synthetic fine silica, attapulgus clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite, fullers earth, cottonseed hulls, wheat flour, soybean flour, pumice, tripoli, wood flour, walnut shell flour, redwood flour and lignin.

It is frequently desirable to incorporate a surface active agent in the pesticidal compositions of the present invention. Such surface active or wetting agents are advantageously employed in both the solid and liquid compositions. The surface active agent can be anionic, cationic or non-ionic in character.

Typical classes of surface active agents include alkyl sulfonate salts, alkylaryl sulfonate salts, a'lkyl sulfate salts, alkylamide sulfonate salts, alkyla-ryl polyether alcohols, fatty acid esters of polyhydric alcohols and the alkylene oxide addition products of such esters, and addition products of long chain mercaptans and alkylene oxides. Typical examples of such surface active agents include the sodium alkylbenzene sulfonates having 10 to 18 carbon atoms in the alkyl group, alkylphenol ethylene oxide condensation products, e.g., p-isooctylphenol condensed with 10 ethylene oxide units, soaps, e.g., sodium stearate and potassium oleate, sodium salt of propylnaphthalene sulfonic acid, (di-Z-ethylhexyl) ester of sodium sulfosuccinic acid, sodium lauryl sulfate, sodium salt of the sulfonated mon-oglyceride of cocoanut fatty acids, sorbitan sesquioleate, lauryl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, polyethylene glycol lauryl ether, polyethylene esters of fatty acids and rosin acids, e.g., Ethofat 7 and 13, sodium N-methyl-N-oleyltaurate, Turkey red oil, sodium dibutylnaphthalene sulfonate, sodium lignin sulfonate (Marasperse N), polyethylene glycol stearate, sodium dodecylbenzene sulfonate, tertiary dodecyl polyethylene glycol thioether (nonionic 218), long chain ethylene oxide-propylene oxide condensation products, e.g., Pluronic 61 (molecular weight 1000), sorbitan sesquioleate, polyethylene glycol ester of tall oil acids, sodium octyl phenoxyethoxyethyl sulfate, tris (polyoxyethylene) sorbitan monostearate (Tween 60), sodium dihexyl sulfosuccinate.

The solid and liquid formulations can :be prepared by any of the conventional procedures. Thus, the active ingredient can be mixed with the solid carrier in finely divided form in amounts small enough to preserve the free-flowing property of the final dust composition.

Bis (1,2-dichloroethyl) sulfone is useful for many different fungicidal purposes. Thus it can be employed not only as a soil fungicide but also as a foliar fungicide, a seed protectant and a seed disinfectant. While some differences have been noted in the activity of the two isomeric forms of the compound, 'both forms are very effective as fungicides and nematocides.

Unless otherwise indicated all are by weight.

It has been observed in the preparation of bis (1,2-dichloroethyl) sulfone that prolonged ultraviolet light treatment tends to favor formation of a higher melting isomer, presently called the gauche isomer whereas shorter ultraviolet light treatment favors formation of the lower melting or trans isomer.

The bis (1,2-dichloroethyl)sulfone is conveniently prepared by chlorinating divinyl sulfone, as shown, for example, by Kliger in J. Gen. Chem. (USSR), 3, 904-908 (1933).

parts and percentages Example 1 10 grams (0.085 mole) of divinyl sulfone was dissolved in 100 ml. of carbon tetrachloride. Into this solution was introduced 12 grams of chlorine (0.17 mole). This was irradiated periodically with a sun lamp until the yellow chlorine color disappeared. The temperature was maintained at less than 40 C. The addition of chlorine gas required ll /2 hours. A white semi-solid was observed in the carbontetrachloride solution.

The entire solution was vacuum stripped. The weight of the light yellow oil and white semi-solid together was 21 grams yield). The product obtained contained small amounts of polymeric divinyl sulfone impurities and was a mixture of the gauche and trans isomers of bis (1,2-dichloroethyl) sulfone; it was given the code number 4244.

Example 2 Over a period of approximately 5 hours there were introduced 7 moles (497 grams) of dry chlorine gas into a solution of 3.5 moles (415 grams) of divinyl sulfone in 2 liters of dry carbontetrachloride with continued irradiation by means of a conventional laboratory sun lamp with mechanical agitation at a temperature of between 35 and 40 C.

A total of 779 grams of a syrup containing oil were obtained which amounted to a yield of 86% calculated for the 3.5 moles of divinyl sulfone originally used. The obtained product was 1,2-dich1oroethyl sulfone, purified by CCL; extraction and evaporation, percent Cl 53.6 found, 54.2% calculated. The crude material contained 8% polymeric divinyl sulfone.

Example 3 Bis (1,2-dichloroethyl) sulfone in the high melting form was prepared by prolonged irradiation with a sun lamp ('8 hours total) as follows:

Into 700 ml. of dry CCL, there was absorbed 80 grams (10% excess over 1 mole) of dry chlorine gas at ice-water bath temperature. The carbon tetrachloride solution was then irradiated with a conventional sun lamp for 1 hour before 59.1 grams (0.5 mole) of divinyl sulfone was added dropwise with stirring, cooling and continued irradiation over a period of one further hour. Continued irradiation over a period of six further hours completed the reaction. Removing the solvent and excess chlorine in high vacuum gave 120 grams (93% yield) of crude product as a solid containing syrup which was free of polymeric divinyl sulfone, percent Cl 53.7 found, 54.2 calculated.

Filtration of this and washing with petroleum ether gave 35 grams of a high melting solid, M.P. 86 C. which later (on standing) melted at 96-99 C., and 53 grams of an oil which crystallized to a low melting solid M.P. 4244 C. The product thus consisted of about 40% of the high melting form and 60% of the low melting form of his (1,2-dichloroethyl) sulfone. The mixture of high and low melting isomers is identified hereinafter as compound 4244.

Example 4 The procedure was essentialy the same as in Example 3 except the irradiation time was reduced to 2.5 hours. As a result, there was formed the low melting form of his (1,2-dichl0roethyl) sulfone predominating in the trans isomer.

A total of 160 grams (2 moles, 11% excess) of dry chlorine gas were absorbed in 1400 ml. of dry carbontetrachloride with ice-water bath cooling, 118.2 grams (1.0 mole) of divinyl sulfone were then added to this carbontetrachloride-chlorine solution dropwise with stirring, irradiation by means of a sun lamp and occasional cooling over a period of one hour. The reaction temperature was maintained between 35 and 45 C. 1.5 hours of additional irradiation with the sun lamp at room temperature (30 C.), removing the solvent and excess chlorine gas gave 234 grams (90% yield) of a greyish-brown syrup which after repeated washing with Skelly Solvent B (a hydrocarbon solvent) gave 199 grams (77% overall yield) of low melting bis (1,2-dichloroethyl) sulfone, M.P., 42- 43 C.

Comparison of the IR spectrum for the enriched gauche isomer (prepared in Example 3) and for the enriched trans isomer (prepared in Example 4) was indicative of stereo isomerism.

The main differences in IR spectra of the gauche and trans isomers is the presence in the gauche spectrum of an additional peak at 1020-1040 cm.-1, an additional peak at 800 cm.-l, an additional peak at 700 cm.-l and a different peak relation between the two isomers at 710 cm.-1 and 715 cm.-1.

Analysis of the NMR spectra of the high melting prod not in Example 3 and the low melting product in Example 4 showed that the high melting product was 76% gauche isomer and 24% trans isomer whereas the low melting product was 32% gauche isomer and 68% trans isomer.

In Examples 1-4 irradiation was carried out with a standard GE sun lamp (25) 275 w., 110-125 v., 60 cycle AC. In Example 5 below there was used a UV source Which produced 90% light of 2537 A. This source was of the NF [JV-300, Nester Faust type, which was inserted directly into the reaction zone.

Example 5 1400 cc. of dry carbontetrachloride were placed in a 3 liter flask fitted with the described UV source, reflux condenser (Dry Ice trap type), stirrer, thermometer and gas inlet tube and cooled to O10 C. 142 grams (2 moles) of dry chlorine gas were then absorbed in the carbontetrachloride at below 10 C. Over a period of approximately one hour, UV irradiation was started and the addition of a total of 118.2 grams (1 mole) of divinyl sulfone started 30 minutes thereafter. The total addition time of the divinyl sulfone was 45 minutes at an average temperature of 20-25" C. (cooling with ice water). After a 21 hour irradiation period, the whole was evaporated under reduced pressure, finally in high vacuum and 241.5 grams (93%) crude 4244 was obtained as a faintly yellow syrup. The latter on treatment with carbontetrachloride gave a total of 25 grams (approximately 10%) of high melting form, M.P. 108 C. and given the code number 5644. IR and NMR spectra revealed that it was the pure gauche form.

The remainder of approximately 215 grams was a faintly colored heavy oil which was given the number 5 645 The NMR spectrum showed it was an approximately trans form containing mixture. It deposited small quantities of crystals (guache form 5644) on prolonged standing, and the trans form in this mixture was eventually better than In the following examples illustrating fungicidal and nematocidal activity, the his (1,2-dichloroethyl) sulfone in some instances was formulated as a wettable powder consisting of 50% of the sulfone, 46% ultrafine silica powder, 2% sodium lignin sulfonate and 2% Pluronic L 61 (polyethylene oxide-polypropylene oxide dduct molecular weight about 1000). This wettable powder is hereinafter designated as Formulation A.

Example 6 Compound 4244, his (1,2-dichloroethyl) sulfone mixed isomers, was dissolved in acetone to give a 1% solution and was then applied to agar cultures of the indicated fungi to determine fungicidal activity. In the table, 10 indicates effectiveness and 0 indicates no effectiveness. The concentrations are expressed in parts per million of the sulfone.

Ooncen- R. solani Pythimn Fusarlum Helmi'nth. tration irr. sativum The sulfone was particularly effective against pythium, a soil inhabiting fungus.

Example 7 replicates of each type of the plant were used. The average growth was 2192 grams. In contrast the average growth of greens of untreated radish, beets and mustard plants in the same period on this soil was 1152 grams for 4 replicares of each species.

Example 8 Bis (1,2-dichloroethyl) sulfone (compound 4244) was tested as a saprophytic nematocide against Panagrellus and Rhabditis spp. in water at room temperature. The

results were recorded as percent kill after a two-day incubation period. The blank mortality was 10% kill.

Example 9 The parasitic nematode test was carried out on agar as the medium with Meloidogyne sp. at room temperature. Infested roots of tomato plants were first treated in the presence of soil for 24 hours with the his (1,2-dichloroethyl) sulfone at the indicated rate of application, transferred onto a previously prepared agar plate and small quantities of water applied to form an aqueous film for the nematodes to disperse on the agar surface. The readings were taken after a period of seven days. At a rate of 25 ppm. there was an 88% mortality and at a rate of 12.5 ppm. there was a 51% mortality.

Example 10 Example 12 Compounds 5644 and 5645 were tested as saprophytic nematocides against Rhabditis spp. in the manner described in Example 8 with the following results expressed in percent kill.

Compound 200 100 50 25 12.5

p.p.m. p.p.m. ppm. p.p.m. p.p.m.

Example 1 3 Compound 5644 and 5645 were tested as fungicides in plate tests in a manner similar to Example 6 with the following results:

Fusarlm 01y. Helmin. Pylhium Rliiz.

Compound Rate sativum irr. solam' lycoperaici References Cited UNITED STATES PATENTS 6/1964 Hensley et al. 16722 5/1966 Aichenegg et a1. 167-22 ALBERT T. MEYERS, Primary Examiner. JULIAN S. LEVITT, SAM ROSEN, Examiners. G. A. MENTIS, J. D. GOLDBERG, Assistant Examiners. 

1. A METHOD OF KILLING NEMATODES COMPRISING APPLYING TO THE NEMATODES BIS (1,2-DICHLOROETHYL) SULFONE. 